CN112280248A - Cobalt ferrite/boron nitride/epoxy resin heat conduction material and preparation method thereof - Google Patents
Cobalt ferrite/boron nitride/epoxy resin heat conduction material and preparation method thereof Download PDFInfo
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- CN112280248A CN112280248A CN202011195050.1A CN202011195050A CN112280248A CN 112280248 A CN112280248 A CN 112280248A CN 202011195050 A CN202011195050 A CN 202011195050A CN 112280248 A CN112280248 A CN 112280248A
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 86
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 65
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 65
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 34
- 239000010941 cobalt Substances 0.000 title claims abstract description 34
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 32
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 239000002135 nanosheet Substances 0.000 claims abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910003321 CoFe Inorganic materials 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract 1
- 239000002114 nanocomposite Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- -1 BN compound Chemical class 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention belongs to the technical field of heat conduction materials, and particularly relates to a preparation method of a cobalt ferrite/boron nitride/epoxy resin heat conduction material, which comprises the following steps: (1) stripping BN powder to obtain a BN nanosheet; (2) dispersing the BN nanosheets to obtain a BN nanosheet dispersion liquid; adding a cobalt source and an iron source into the BN nanosheet dispersion liquid, and uniformly mixing to obtain a mixed liquid; dropping alkali liquor into the mixed liquor, heating to 60-90 ℃, preserving heat, collecting precipitate after heat preservation, washing and drying to obtain CoFe2O4a/BN complex; (3) mixing CoFe2O4Ultrasonic separation of/BN complexesDispersing in water, adding into liquid epoxy resin, and distilling under reduced pressure to obtain cobalt ferrite/boron nitride/epoxy resin mixed solution; adding a curing agent, stirring under ice bath and vacuum conditions, pouring into a mold, and curing under the action of a magnetic field to obtain the cobalt ferrite/boron nitride/epoxy resin heat conduction material.
Description
Technical Field
The invention belongs to the technical field of heat conduction materials, and particularly relates to a cobalt ferrite/boron nitride/epoxy resin heat conduction material and a preparation method thereof.
Background
Epoxy resins are widely available and include bisphenol a epoxy resins, aliphatic epoxy resins, novolac epoxy resins, etc., with bisphenol a epoxy resins being the most widely used class of epoxy resins. However, the following problems are present in the epoxy resin for electronic and electrical applications: firstly, the thermal conductivity is poor, the thermal conductivity coefficient of the epoxy resin is low (less than 0.2W/m.K), and the generated heat cannot be dissipated in time; secondly, the impact resistance is poor, the toughness is low, the texture is crisp, and the impact resistance is insufficient.
In the prior art, the thermal conductivity of the epoxy resin is improved mostly by the thermal conductive filler. The heat-conducting filler is mainly inorganic heat-conducting filler and comprises metal filler, oxide filler, carbon material and heat-conducting nitride filler. Boron Nitride (BN) can effectively improve the thermal conductivity of the epoxy resin while maintaining excellent insulation properties of the epoxy resin. However, boron nitride is randomly distributed in the epoxy resin, and the improvement of the thermal conductivity of the epoxy resin is limited.
Disclosure of Invention
Based on the defects in the prior art, the invention provides a cobalt ferrite/boron nitride/epoxy resin heat conduction material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a cobalt ferrite/boron nitride/epoxy resin heat conduction material comprises the following steps:
(1) adding BN powder into the stripping solution to perform hydrothermal reaction to obtain a reaction product; sequentially carrying out ultrasonic dispersion and centrifugation on the reaction product to obtain a suspension containing BN nanosheets; carrying out suction filtration and drying on the suspension containing the BN nanosheets to obtain the BN nanosheets;
(2) dispersing the BN nanosheets to obtain a BN nanosheet dispersion liquid; adding a cobalt source and an iron source into the BN nanosheet dispersion liquid, and uniformly mixing to obtain a mixed liquid; dropping alkali liquor into the mixed liquor, heating to 60-90 ℃, preserving heat, collecting precipitate after heat preservation, washing and drying to obtain CoFe2O4a/BN complex;
(3) mixing CoFe2O4the/BN compound is ultrasonically dispersed in water and then added into liquid epoxy resin for reduced pressure distillation to obtain a cobalt ferrite/boron nitride/epoxy resin mixed solution; adding a curing agent into the cobalt ferrite/boron nitride/epoxy resin mixed solution, and stirring under ice bath and vacuum conditions to obtain an epoxy resin mixed system; and pouring the epoxy resin mixed system into a mold, and curing under the action of a magnetic field to obtain the cobalt ferrite/boron nitride/epoxy resin heat conduction material.
Preferably, the CoFe2O4CoFe in/BN composite2O4Molar ratio to BN 1: 1 to 5.
Preferably, the CoFe2O4The content of the/BN composite in the cobalt ferrite/boron nitride/epoxy resin heat conduction material is 2.5-20 wt%.
Preferably, the strength of the magnetic field is 100 to 300 mT.
Preferably, in the step (1), the stripping solution is one or more of a tetramethylammonium hydroxide solution, an ammonium hydroxide solution, a tetraethylammonium hydroxide solution, a tetrapropylammonium hydroxide solution, and a tetrabutylammonium hydroxide solution.
Preferably, in the step (1), the hydrothermal reaction conditions include: the reaction temperature is 160-180 ℃, and the reaction time is at least 6 h.
Preferably, in the step (1), the rotation speed of the centrifugation is 1500-3000 rpm.
Preferably, in the step (2), the cobalt source is at least one of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt sulfate, the iron source is at least one of ferric nitrate, ferric chloride and ferric sulfate, and the alkali solution is at least one of NaOH solution and KOH solution.
Preferably, in the step (3), the reduced pressure distillation conditions are as follows: the temperature is 70-100 ℃, and the time is 4-8 hours; the curing agent is 593 curing agent, GY-051 curing agent, 590 curing agent, 701 curing agent, 702 curing agent, 703 curing agent or 120 curing agent.
The invention also provides a cobalt ferrite/boron nitride/epoxy resin heat conduction material prepared by the preparation method of any one of the schemes.
Compared with the prior art, the invention has the beneficial effects that:
the cobalt ferrite/boron nitride/epoxy resin heat conduction material provided by the invention grows CoFe on the surface of the stripped BN nano-sheet in situ2O4And regulating and controlling CoFe by magnetic field2O4The orientation arrangement of the/BN compound in the epoxy resin is realized, and a high-efficiency heat conduction channel is constructed in the epoxy resin matrix; based on CoFe2O4The heat conductivity of the BN nano sheet is between that of BN and epoxy resin, so that the interface thermal resistance between the BN nano sheet and an epoxy resin matrix is reduced, the heat conductivity and the impact resistance of the epoxy resin are cooperatively improved, and the application range of the epoxy-based heat conduction material in the electrical field is expanded.
Drawings
FIG. 1 is SEM photographs of BN sheet before (A) and after (B) peeling of an example of the invention;
FIG. 2 is CoFe of an embodiment of the present invention2O4SEM photograph and partial enlarged view of/BN nano composite material;
FIG. 3 is a diagram of CoFe of different mass fractions for an example of the present invention2O4A change diagram of the influence of the/BN nano composite material on the heat-conducting property of the cobalt ferrite/boron nitride/epoxy resin heat-conducting material;
FIG. 4 is a graph of CoFe at different mass fractions for an example of the invention2O4And (3) a change graph of impact performance influence of the/BN nano composite material on the cobalt ferrite/boron nitride/epoxy resin heat conduction material.
Detailed Description
The technical solution of the present invention is further explained by the following specific examples.
Example (b):
the preparation method of the cobalt ferrite/boron nitride/epoxy resin heat conduction material comprises the following steps:
(1) exfoliation of BN
Preparing 50% tetramethylammonium hydroxide solution;
adding 2g of BN powder (about 3 mu m) into 80mL of tetramethylammonium hydroxide solution, transferring the mixture into a 100mL high-pressure reaction kettle, and keeping the temperature at 180 ℃ for 12 hours;
thirdly, after the reaction is finished, cooling to room temperature, collecting and dispersing a solid product in 400mL of deionized water, and performing ultrasonic treatment for 2 hours;
fourthly, after suction filtration, washing the powder with deionized water to be neutral, and dispersing the powder into 200mL of deionized water again;
centrifuging at 2000rpm for 30min to obtain suspension containing BN nanosheets;
sixthly, performing vacuum filtration by using a polypropylene filter membrane (0.8 mu m), and then performing vacuum drying at the temperature of 60 ℃ to obtain BN nanosheet powder.
As shown in fig. 1, the un-peeled BN sheet layers are in a tightly stacked state and thick; after hydrothermal exfoliation, lamellar BN was observed, indicating that the BN powder was exfoliated into BN nanosheets.
(2)CoFe2O4Preparation of/BN nanocomposite
Dispersing 0.1g of BN nanosheet powder in 30mL of deionized water to form BN nanosheet dispersion;
② adding 1mmol (0.582g) of cobalt nitrate hexahydrate and 2mmol (1.616g) of ferric nitrate nonahydrate into the 30mL of BN dispersion, and stirring for 1h to form a uniform mixed solution;
dissolving 20mmol (0.8g) of NaOH in 10mL of deionized water to prepare 2M NaOH solution;
fourthly, dropwise adding the NaOH solution in the third step into the mixed solution in the fourth step, gradually changing the color of the mixed solution to be black, heating to 75 ℃ after dropwise adding, and keeping the temperature for 2 hours;
fifthly, after heat preservation, centrifuging and concentrating for 5min at 4000rpm, and collecting precipitates;
sixthly, washing the collected precipitate with water and ethanol for 3 times respectively, removing NaOH and other impurities, vacuum drying at 80 ℃ for 12 hours,obtaining CoFe2O4a/BN nanocomposite. As shown in FIG. 2, CoFe is successfully grown in situ on the surface of the BN nanosheet2O4And (3) nanoparticles.
(3) Cobalt ferrite (CoFe)2O4) Preparation of Boron Nitride (BN)/epoxy resin (EP) heat conduction material
Firstly, the obtained CoFe2O4Adding the/BN nano composite material into the aqueous solution, performing ultrasonic dispersion, then adding the mixture into liquid epoxy resin, performing reduced pressure distillation at 80 ℃ for 6 hours to obtain a cobalt ferrite/boron nitride/epoxy resin mixed solution, then adding 593 curing agent, and stirring under ice bath and vacuum conditions to obtain an epoxy resin mixed system; wherein, the vacuum condition is used for exhausting bubbles, so that the structural compactness of the cured material is ensured.
Pouring the epoxy resin mixed system prepared in the step I into a stainless steel mold, and curing the epoxy resin mixed system under the magnetic field with the strength of 200mT to obtain the cobalt ferrite/boron nitride/epoxy resin heat conduction material.
Research on the cobalt ferrite/boron nitride/epoxy resin heat conduction material (directional CoFe for short) of the embodiment2O4CoFe in/BN/EP)2O4The influence of the mass fraction of the/BN composite material on the heat-conducting property and the impact property of the cobalt ferrite/boron nitride/epoxy resin heat-conducting material.
As shown in FIG. 3, with CoFe2O4The mass fraction of the/BN composite material is increased, and the heat conductivity coefficient of the heat conduction material is continuously increased; wherein, disordered CoFe2O4BN/EP and oriented CoFe2O4The difference between the/BN/EP lies in that the solidification process is not carried out under the action of a magnetic field, and disordered CoFe2O4The thermal conductivity is higher for/BN/EP than for BN/EP, because CoFe2O4Addition of (1), CoFe2O4The thermal conductivity coefficient of the composite is between BN and EP, so that the interface thermal resistance between the BN nanosheet and the epoxy resin matrix is reduced, and the thermal conductivity coefficient is improved. For disordered CoFe2O4BN/EP, oriented CoFe2O4The thermal conductivity of/BN/EP is higher because CoFe is regulated by magnetic field2O4Use of/BN complexes in epoxy treesThe directional arrangement of the interior of the grease builds a high-efficiency heat conduction channel in the interior of the epoxy resin matrix, thereby further improving the heat conduction performance.
As shown in FIG. 4, with CoFe2O4The mass fraction of the/BN composite material is increased, the impact strength of the heat conduction material is increased firstly and then reduced, and the impact strength of the heat conduction material is increased after the impact strength of the heat conduction material is reduced in CoFe2O4The mass fraction of the/BN composite material reaches the highest about 5 wt%, because the high filling content can cause CoFe2O4the/BN composite material generates agglomeration in an epoxy resin matrix, thereby reducing CoFe2O4Impact resistance of/BN/EP. In addition, disordered CoFe2O4The impact performance of the BN/EP is not greatly different from that of the BN/EP, and is even reduced; and oriented CoFe2O4The impact strength of the/BN/EP is better, which is mainly attributed to: in oriented CoFe2O4in/BN/EP, CoFe2O4The oriented arrangement of the/BN composite material can better bear and dissipate stress.
In the above examples and alternatives, CoFe2O4CoFe in/BN composite material2O4The molar ratio to BN may also be 1: 1. 1: 2. 1: 3. 1: 4, etc.
In the above embodiments and alternatives, the magnetic field may also have a strength of 100mT, 150mT, 250mT, 300mT, etc., and nanoparticles that are too weak in magnetic field may not be oriented and too strong may easily cause particle agglomeration.
In the above embodiments and alternatives, the tetramethylammonium hydroxide solution may be a plurality of solutions selected from the group consisting of an ammonium hydroxide solution, a tetraethylammonium hydroxide solution, a tetrapropylammonium hydroxide solution, and a tetrabutylammonium hydroxide solution, and the tetramethylammonium hydroxide solution, the ammonium hydroxide solution, the tetraethylammonium hydroxide solution, the tetrapropylammonium hydroxide solution, and the tetrabutylammonium hydroxide solution as the stripping solution.
In the above embodiments and alternatives, the reaction temperature of the hydrothermal reaction may be 160 ℃, 165 ℃, 170 ℃, 175 ℃ and the like, and the reaction time may be 6h, 12h, 20h, 48h and the like.
In the above embodiment and its alternatives, the rotation speed of the centrifuge during the peeling of BN may also be 1500rpm, 2500rpm, 3000rpm, etc.
In the above embodiment and its alternatives, the cobalt source may also be cobalt chloride, cobalt acetate, or cobalt sulfate, or may also be multiple of cobalt nitrate, cobalt chloride, cobalt acetate, or cobalt sulfate, the iron source may also be ferric chloride or ferric sulfate, or may also be multiple of ferric nitrate, ferric chloride, or ferric sulfate, and the alkali solution may also be a KOH solution or a mixed solution of a NaOH solution and a KOH solution.
In the above examples and alternatives, CoFe2O4In the preparation process of the/BN nano composite material, the temperature of the temperature rise in the step (IV) can be 60 ℃, 65 ℃, 80 ℃, 85 ℃, 90 ℃ and the like.
In the above embodiments and alternatives, the temperature of the reduced pressure distillation may be 70 ℃, 85 ℃, 90 ℃, 100 ℃ and the like, and the time may be 4 hours, 7 hours, 8 hours and the like; the curing agent can also be GY-051 curing agent, 590 curing agent, 701 curing agent, 702 curing agent, 703 curing agent or 120 curing agent.
The "/" in the present invention means "and".
The foregoing has outlined rather broadly the preferred embodiments and principles of the present invention and it will be appreciated that those skilled in the art may devise variations of the present invention that are within the spirit and scope of the appended claims.
Claims (10)
1. A preparation method of a cobalt ferrite/boron nitride/epoxy resin heat conduction material is characterized by comprising the following steps:
(1) adding BN powder into the stripping solution to perform hydrothermal reaction to obtain a reaction product; sequentially carrying out ultrasonic dispersion and centrifugation on the reaction product to obtain a suspension containing BN nanosheets; carrying out suction filtration and drying on the suspension containing the BN nanosheets to obtain the BN nanosheets;
(2) dispersing the BN nanosheets to obtain a BN nanosheet dispersion liquid; adding a cobalt source and an iron source into the BN nanosheet dispersion liquid, and uniformly mixing to obtain a mixed liquid; dropping alkali liquor into the mixtureHeating the mixed solution to 60-90 ℃ for heat preservation, collecting precipitates after heat preservation, washing and drying to obtain CoFe2O4a/BN complex;
(3) mixing CoFe2O4the/BN compound is ultrasonically dispersed in water and then added into liquid epoxy resin for reduced pressure distillation to obtain a cobalt ferrite/boron nitride/epoxy resin mixed solution; adding a curing agent into the cobalt ferrite/boron nitride/epoxy resin mixed solution, and stirring under ice bath and vacuum conditions to obtain an epoxy resin mixed system; and pouring the epoxy resin mixed system into a mold, and curing under the action of a magnetic field to obtain the cobalt ferrite/boron nitride/epoxy resin heat conduction material.
2. The method of claim 1, wherein the CoFe is2O4CoFe in/BN composite2O4Molar ratio to BN 1: 1 to 5.
3. The method according to claim 1 or 2, wherein the CoFe2O4The content of the/BN composite in the cobalt ferrite/boron nitride/epoxy resin heat conduction material is 2.5-20 wt%.
4. The method according to claim 1, wherein the magnetic field has a strength of 100 to 300 mT.
5. The method according to claim 1, wherein in the step (1), the stripping solution is one or more of a tetramethylammonium hydroxide solution, an ammonium hydroxide solution, a tetraethylammonium hydroxide solution, a tetrapropylammonium hydroxide solution, and a tetrabutylammonium hydroxide solution.
6. The method according to claim 1, wherein in the step (1), the hydrothermal reaction conditions include: the reaction temperature is 160-180 ℃, and the reaction time is at least 6 h.
7. The method according to claim 1, wherein in the step (1), the rotation speed of the centrifuge is 1500 to 3000 rpm.
8. The preparation method according to claim 1, wherein in the step (2), the cobalt source is at least one of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt sulfate, the iron source is at least one of ferric nitrate, ferric chloride and ferric sulfate, and the alkali solution is at least one of NaOH solution and KOH solution.
9. The production method according to claim 1, wherein in the step (3), the conditions of the reduced pressure distillation are as follows: the temperature is 70-100 ℃, and the time is 4-8 hours; the curing agent is 593 curing agent, GY-051 curing agent, 590 curing agent, 701 curing agent, 702 curing agent, 703 curing agent or 120 curing agent.
10. A cobalt ferrite/boron nitride/epoxy resin heat conductive material, characterized by being prepared by the preparation method of any one of claims 1 to 9.
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